The present invention relates to a process of replenishing a color developing solution for a light-sensitive silver halide color photographic material, more specifically to a process for replenishing a color developing solution with replenisher compositions which process can dissolve a poorly soluble alcohol uniformly, easily and in a short time, and also suitable for the AR system (which will be explained hereinafter).
A color developing solution which is used for processing a light-sensitive silver halide color photographic material usually contains such developer components as represented by a p-phenylenediamine derivative or a salt thereof as a color developing agent; a carbonate, a borate or a phosphate as an alkaline agent; a sulfite or a hydroxylamine salt as a preservative; and so on. It further contains, as occasion demands, a poorly soluble alcohol as a development accelerator, for example, benzyl alcohol or the like.
When such a color developing solution is used continuously and its use is over a long period of time, the main component thereof is consumed and an added component (additive) is dissolved out of a light-sensitive material to be processed. As the result, the activity of the color developing solution is lost and the obtained image properties are subject to deterioration.
Thus, for the purpose of replenishing the developing components which have been lost by the above-mentioned continuous processing and of diluting the additive components which have been dissolved out of the light-sensitive material, there has been taken a procedure in which a color developing replenisher is prepared and supplemented in necessary portions to the above-mentioned color developing solution.
Recently, on account of economy and of the social demand to minimize any pollutive component which is caused by the waste developing solution to be discharged during the developing process, there is a tendency that the replenisher for a color developing solution be thickened or concentrated and the amount thereof reduced. In order to save labor for the mixing and dissolving operations of chemical agents for a developing solution or to concentrate and minimize the replenishing amount, the necessity is expanding for a concentrated supplemental developing solution capable of easy preparation only by diluting with water.
However, a poorly soluble alcohol, e.g., benzyl alcohol etc., to be used as a development accelerator has extremely poor solubility in water or a color developing solution, it has required a fairly long time for the replenisher composition to dissolve thoroughly, and vigorous stirring and heating have frequently been required.
In cases where the dissolution of such poorly soluble alcohol is insufficient, there is observed phenomena of oil-drops being formed in the developing solution (oil-out) and floating at the surface thereof.
This causes smears in a color developer tank, a replenisher tank or a mixing tank of an automatic processing machine which is used for the processing, and further causes a change in a practical composition of a developing solution to exert an adverse effect upon photographical processing performance, which has been problematic.
For the purpose of improving the above drawbacks, there are proposed methods of preparing an aqueous dispersion by using glycols such as ethylene glycol as described in the specification of U.S. Pat. No. 3,574,615 and so on or by using celluloses such as hydroxyethyl cellulose as described in the specification of U.S. Pat. No. 3,615,496 and so on to disperse above-mentioned poorly soluble alcohol.
However, in cases where a glycol mentioned above is used, 10 g or more of the same is required per 1 lit. of the color developing solution, which results in remarkable increase of B.O.D. (Biochemical Oxygen Demand) or C.O.D. (Chemical Oxygen Demand) in the color developing solution. This is not only undesirable in view of the prevention of pollution but also disadvantageous economically.
On the other hand, in cases where a cellulose is used as has been done conventionally, it has a property capable of dispersing and solubilizing the poorly soluble alcohol with a relatively small amount thereof. However, a large amount of water is necessary to obtain a uniform replenisher composition leading to a large volume of a replenisher composition. Further, since a small amount of water cannot provide any uniform replenisher composition, there is a drawback in that a part of such non-uniform replenisher composition cannot be taken out for replenishment.
There has recently been adopted an AR system (Automatic Replenishing System) in which various parts of processing agents and a dilution kit are connected with each other and the solutions are automatically diluted and mixed with water followed by replenishing a processing tank of an automatic processing machine, for the purposes of simplifying the operation for dissolving the processing agents and of labor-saving.
However, since a poorly soluble alcohol, such as benzyl alcohol etc. is extremely inferior in solubility, a mixing room and a mixing device are always provided with said AR system. So the AR system carries a problem that it fails to be compact as a device.
Thus, an object of the present invention is primarily to provide a process for replenishing a developing solution with a replenisher composition, which process is capable of dissolving a poorly soluble alcohol uniformly, easily and within a short time in the replenishment of the color developing solution, secondarily to provide a process for replenishing a color developing solution with a replenisher composition, wherein each part has an excellent solubility to realize a compact AR system without any necessity of a mixing device and so on.